© Copyright 2001 by the American Chemical Society
VOLUME 105, NUMBER 47, NOVEMBER 29, 2001
Biography of Howard Reiss Howard Reiss was born in New York City in 1922. In 1939 he entered New York University, at what was then the University Heights Campus, where he majored in Chemistry and graduated Magna Cum Laude in 1943, receiving a B.A. with Honors in Chemistry. During his senior year, under the tutelage of Professor H. G. Lindwall, he performed research on reactions and preparations of the methylindoles. Upon graduation he was awarded a teaching fellowship at Princeton University where he decided to change direction and study physical rather than organic chemistry. He began to work, with Professor John Turkevich, on catalytic mechanisms of cyclization of olefins to form xylenes. In 1944 his graduate studies at Princeton were cut short, after less than a year, by induction into the U. S. Army. After completing basic training at Fort Leonard Wood in Missouri, he was assigned to the Special Engineer Detachment of the Army Engineers and sent to Oak Ridge where he worked on the Manhattan Project. In the interim he married Phyllis Felicia Kohn who is now his wife of 56 years. He was discharged from the army in 1946. His Ph.D. work was completed at Columbia University where he received a doctorate in 1949. His thesis, concerned with both experiment and theory, addressed problems in the nucleation and growth of monodis-
perse aerosols and hydrosols, and was performed under the direction of Professor V. K. LaMer. In 1949 Reiss was appointed to the position of Instructor in the Chemistry Department of Boston University. There he performed cloud chamber work on nucleation, but he also published three seminal papers, one on “Nucleation in Binary Systems” (1950), another on the “Growth of Uniform Colloidal Dispersions” (1951) and a third on “Studies of the Evaporation of Small Drops” (1954) with L. Monchick. The work on binary systems provided, for the first time, formulas for the growth flux of multicomponent clusters through a demonstrated saddle point on an associated free energy landscape, while the paper on colloidal dispersions provided a mechanistic explanation for the diffusional growth of monodisperse colloids. The paper on evaporation pioneered the study of the evaporation of drops (before the era of electrodynamic levitation) by suspending them in a Milliken oil drop apparatus. Unique aspects of the study were that the drops were smaller than the mean free path in the surrounding medium and that effects of the Kelvin relation for the vapor pressure of a small drop were observed. In 1951 he left Boston University to join the Staff of the Celanese Reserch Laboratory in Summit New Jersey and, after
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11534 J. Phys. Chem. B, Vol. 105, No. 47, 2001 a year at Celanese, he moved to nearby Bell Laboratories where he remained until 1960. At Bell he had the opportunity to learn “solid state” and was able to publish several important papers. These included “Chemical Interactions among Defects in Germanium and Silicon” (1956) with C. S. Fuller amd F. J. Morin, “The Ionization of Hydrogen and Lithium in Germanium and Silicon” (1956), and “Statistical Mechanics of Rigid Spheres” (1959) with H. L. Frisch and J. L. Lebowitz. His work on chemical-like interactions, both experimental and theoretical, demonstrated the role of the elemental semiconductors as media analogues for water in which electrons and holes could play the roles of hydrogen and hydroxyl ions and in which ion pairing could occur and also provided a nontransport method for measuring band structure. The paper on the ionization of hydrogen and lithium provided a quantum-mechanical explanation for the ionization of interstitial lithium, and the nonionization of interstitial hydrogen, in germanium and silicon, thus accounting for the initial failure of workers to detect hydrogen as an impurity in these substances. The paper on rigid spheres marked the emergence of the “Scaled Particle theory”, which remains a tool in the statistical mechanics of fluids. While at Bell Laboratories, Reiss worked in several other areas including device physics and, with its inventor William G. Pfann, on zone melting. He is responsible for most of the differential equations that characterize zone melting. In 1960 he left Bell Laboratories to join the staff of Atomics International located in Los Angeles. Atomics International was the smallest division of North American Aviation, later to become Rockwell International. Atomics International specialized in central station power reactors and, in particular, on a sodium cooled reactor. Within a year of his arrival at the company, through an unexpected set of events he was appointed to the post of Director of Research for the Division. Even less expected and without management experience, within the next year, he was chosen to build and head a newly planned central research laboratory, the North American Aviation Science Center. He undertook this task and by 1963 the new center had been built and occupied in Thousand Oaks, CA. North American Aviation featured a broad range of advanced technologies, including military aircraft, ballistic missiles, computers and solid state electronics, rocket engines, nuclear power, and space systems. The company became the prime contractor for the Apollo program and for the development of the space shuttle. Myriad diversified scientific disciplines supported these technological activities, and the Science Center devoted itself to the pursuit of fundamental research in these disciplines while at the same time developing philosophy and procedures for impacting the associated technologies. Only central funds and not individual contracts supported the research effort. An outstanding scientific staff was rapidly acquired, and many of these staff members are now well-known scientists, especially in academia. The Science Center was given divisional status and Howard Reiss, acquiring the title of Divisional President, reported directly to the Chief Executive Officer and Chairman of the board, J. L. Atwood. Eventually, he was elected to the rank of Vice President and served as a corporate officer although he still directed the Science Center. He remained in this position until 1968 when he joined the faculty of the Department of Chemistry and Biochemistry at UCLA as a Full Professor. The Science Center persists as the Rockwell International Science Center, but its thrust is vastly different from its role as part of North American Aviation. His management responsibilities at North American Aviation understandably limited Reiss’s personal scientific activities. Still,
he was able to perform some significant research during his eight-year tenure at North American. Important papers during this period included work on fused salts, namely (1) “Theory of the Surface Tension of Molten Salts” (1961) with S. W. Mayer, (2) “Law of Corresponding States for Fused Salts” (1961) with S. W. Mayer and J. L. Katz, and (3) “Theory of the Heats of Mixing of Certain Fused Salts” (1962) with J. L. Katz and O. Kleppa. These “scaling” theories dealing with the thermodynamics of fused salts are still used today. In a field that is now known as random sequential adsorption (RSA) he published, with E. R. Cohen, what is now recognized as an early classic, “Kinetics of Reactant Isolation I. One-Dimensional Problems” (1963). In the field of nucleation he published (1) “Nucleation in Associated Vapors” (1966) with J. L. Katz and H. Saltsburg and (2) “Translation-Rotation Paradox in the Theory of Nucleation” (1968) with J. L. Katz and E. R. Cohen. These last two papers were pioneering efforts in both areas. In particular, the second paper was a first rational attempt to deal with the translational free energy problem in the classical theory of nucleation. Reiss published other papers while at North American. These involved melting of copolymeric DNA, theories of epitaxy, and segregation of solutes in stressed solids. He also wrote on research management. Finally, while at North American, he wrote his monograph “Methods of Thermodynamics”, first published in 1965 by Blaisdell Press and republished in 1996, in paperback, by Dover Publications. This book, which deals with the problem areas of understanding in thermodynamics, focuses heavily on the role of constraints, a theme that has occupied Howard Reiss until this day. Upon moving to UCLA in 1968, he focused his attention on nucleation phenomena. His interest in nucleation has been a recurrent theme throughout his scientific career. He engaged in both experiment and theory. A set of important studies concerned water and sulfuric acid. Some relevant papers are (1) “Investigation of the Homogeneous Nucleation of Water Vapor Using a Diffusion Cloud Chamber” (1973) with R. H. Heist, (2) “Hydrates in Binary Sulfuric Acid-Water Vapor” (1974) with R. H. Heist, (3) “Theory of Vapor Phase Nucleation in Binary Mixtures of Water and Sulfuric Acid” (1974) with W. J. Shugard and R. H. Heist, and (4) “Hydrates in Supersaturated Binary Sulfuric Acid-Water Vapor: A Reexamination” (1987) with A. Jaecker-Voirol and P. Mirabel. Sulfate aerosols have proved to be a significant deleterious atmospheric component, responsible not only for acid rain and unhealthy mists but also for a stratospheric component that significantly alters the albedo of the earth, and these papers represent pioneering efforts in the field. Of special importance was the realization of the role played by hydrate formation. Reiss was also interested in the possibility of using nucleation in the detection of trace substances in vapor, and in particular, in the use of nucleation to study processes in situ that could not be studied in any other way. One such process was the bimolecular photooxidation of SO2 to SO3 which proceeds so slowly that it is difficult to detect the product by conventional means and impossible in the presence of water vapor. However, the study could be carried out quite expeditiously in supersaturated water vapor in a diffusion cloud chamber. Product H2SO4 nucleates water droplets and the rate of nucleation is related to the rate of photooxidation. Among other things it was discovered that the presence of water vapor accelerates the reaction. The relevant paper is “Cloud Chamber Study of the Gas-Phase Photooxidation of Sulfur Dioxide” (1978) with D. C. Marvin.
J. Phys. Chem. B, Vol. 105, No. 47, 2001 11535 Another such process is true homogeneous gas phase free radical addition polymerization such that growing polymers are retained in the monomer vapor phase. This requires that so few polymers be grown simultaneously that they cannot encounter one another to condense out of the vapor. The detection sensitivity inherent in nucleation makes this feasible. For example, styrene liquid was known to polymerize thermally at room temperature, but the phenomenon could not be observed in the vapor. However, nucleation studies in a diffusion cloud chamber in supersaturated styrene vapor showed that drops of styrene formed, via heterogeneous nucleation, on the few polymers that had been produced by thermal polymerization in the vapor and proved that thermal radical addition polymerization did indeed occur in the vapor, but too slowly to be observed by conventional means. The relevant paper is “Homogeneous Gas PhaseThermal Polymerization of Styrene” (1987) with M. S. El-Shall, A. Bahta, and H. M. Rabeony. In another study conducted in an expansion cloud chamber, it was shown that single oligomers of pol(vinyl acetate) could act as heterogeneous nuclei for the condensation of supersaturated vinyl acetate vapor and that the propagation constant for free radical addition in the vapor was several orders of magnitude smaller than in the liquid. The relevant paper is “Study of Homogeneous Gas-Phase Free radical Addition Polymerization of Vinyl Acetate using Nucleation for Detection” (1994) with P. Jin. During his tenure at UCLA, now in excess of 33 years, Reiss also continued to develop the theory of nucleation. His interest gradually turned to molecular, as opposed to phenomenological, theories of nucleation with emphasis on argon or Lennard-Jones type substances and on the introduction of other order parameters besides molecular content in the description of clusters. Much progress was made via both analytical theory and simulation. A few important recent papers are (1) “Role of the Model Dependent Translational Volume Scale in the Classical Theory of Nucleation” (1998) with W. K. Kegel and J. L. Katz, (2) “A Molecular Theory of the Homogeneous Nucleation Rate II: Application to Argon Vapor” (1999) with B. Senger, P. Schaaf, D. S. Corti, R. K. Bowles, D. Pointu, and J.-C. Voegel, (3) “Some Fundamental Statistical Mechanical Relations Concerning Physical Clusters of Interest to Nucleation Theory” (1999) with R. K. Bowles, (4) “Simulation of Nanoscale Density Fluctuations” (2000) with R. K. Bowles, (5) Simulative Determination of Kinetic Coefficients for Nucleation Rates” (2001) with P. Schaaf, B. Senger, J.-C. Voegel and R. K. Bowles, and (6) “A Theorem for Inhomogeneous Systems: Generalization of the Nucleation Theorem” (2001) with R. K. Bowles, D. Reguera, and Y. Djikaev. All of these papers are important, but the last deserves some additional comment since it transcends the field of nucleation. The “nucleation theorem” is a purely thermodynamic relation that allows one to determine both the excess molecular content and excess entropy associated with a nonuniformity in density induced by an external field (even a virtual field). In particular, it has been used in the determination of the excess number of molecules represented by a nucleus. However, in paper number 6 it is shown that the theorem applies to any nonuniform system and that, although thermodynamic in nature, it remains valid down to the molecular level. At UCLA Reiss also studied a phenomenon related to nucleation, namely the deliquescence of nanoscale atmospheric particles. A relevant paper is “Theory of Size Dependent Deliquescence of Nanoparticles: Relation to Heterogeneous Nucleation and Comparison with Experiments” (2001) with Y. S. Djikaev, R. K. Bowles, K. Hameri, A. Laaksonen, and M. Vakeva.
At UCLA Reiss continued his studies of hard particle systems. Important papers in this area are (1) “Cavities in the Hard Sphere Fluid and Crystal and the Equation of State” (1991) with R. J. Speedy, (2) “Statistical Geometry in the Study of Fluids and Porous Media” (1992), (3) “Depletion Force between a Colloid Particle and a Wall: Simple Theory by Means of Scaled Particle Theory” (1998) with D. S. Corti, and (4) “Magic Relation between the Structures of Coexisting Phases at a First-Order Phase Transition in a Hard Sphere System” (2000). He also became interested in the developing field of conducting polymers, largely as a result of his earlier work with impurities and defects in semiconductors. He studied the uptake of iodine in polythiophene as an analogue of lithium in germanium or silicon with the idea of measuring band structure via an equilibrium experiment. He also worked on the uptake of protons by polyaniline, predicting the uptake curve before its measurement by MacDiarmid et al., and also on the mechanism of p,n-junction formation and light emission in ion containing polymers upon the application of a voltage bias. Relevant papers are (1) “Thermodynamically Reversible Uptake of Electrically Active Dopants in Conducting Polymers: Iodine in Polythiophene” (1988) with D. Kim, (2) “Note on the Protonic Doping of Polyaniline” (1989), and (3) “Polymer Light-Emitting Electrochemical Cells: ATheoretical Study of Junction Formation under Steady-State Conditions” (1998) with J. A. Manzanares and A. J. Heeger. At UCLA, Reiss has worked and published on a wide range of additional topics. These include electrochemistry, ion exchange membranes, bipolar membranes for water splitting, conducting polymer membranes for the separation of gases, information theory, traffic, volume scales for the NPT ensemble, random sequential adsorption, constraints in thermodynamics, and translational entropy in microemulsions and entropy induced dispersion. Lack of space prevents a discussion of all of these topics, but it might be mentioned that his 1975 paper “EntropyInduced Dispersion of Bulk Liquids” was the first treatment of the subject, and his 1983 paper on bipolar membranes with I. C. Bassignana, “Ion Transport and Water Dissociation in Ion Exchange Bipolar Membranes” was the first theory of transport in these membranes. Also his 1996 paper with G. J. M. Koper, “Length Scale for the Constant Pressure Ensemble”, opened a topic that is still subject to some controversy but appears to be on the way to acceptance. In electrochemistry he wrote a definitive paper on the absolute electrode potential, “The Absolute Electrode Potential: Tying the Loose Ends” (1988). Finally, an important collaboration with D. Kivelson led to a definitive study of the role of metastability in thermodynamics and the use of constraints. The published paper is “Metastable Systems in Thermodynamics: Consequences, Role of Constraints” (1999) with D. Kivelson. Among other things it was shown that so-called residual entropy was a consequence of the irreversibility of the apparent glass transition in which “work” was not exchanged with the environment. Reiss’s teaching activities at UCLA included courses in physical chemistry, statistical mechanics, quantum mechanics, colloid chemistry, electrochemistry, polymer chemistry, and general chemistry. He has served on many governmental committees and on the editorial boards of many journals. In fact he is the founding editor both of the Pergamon Press series “Progress in Solid State Chemistry” and of the Journal of Statistical Physics. He has been recognized for his many contributions in multiple ways. Honors include the McCoy award of the UCLA Chemistry Department, the American Chemical Society (ACS) Tolman
11536 J. Phys. Chem. B, Vol. 105, No. 47, 2001 Medal (1973), ACS Kendall Award in Colloid and Surface Chemistry (1980), ACS Hildebrand Award in the Physical Chemistry of Liquids (1991), and the David Sinclair Award of the American Association for Aerosol Research (1997). He is a member of the National Academy of Sciences (1977) and a fellow of both the American Physical Society and the American Association for the Advancement of Sciences. He has also been a Guggenheim Fellow (1979). Recently, he held the (1994) Van Arkel Honorary Chair in Chemistry at Leiden University in The Netherlands. In 1979 the Journal of Statistical Physics published a Festschrift in his honor. In 1991 he became Professor Emeritus at UCLA. In 2000, a “Career Development Chair” endowed by the John P. McTague Family, was established in his name within
the Department of Chemistry and Biochemistry at UCLA Also, in August of the current year a symposium in his honor was held at the 15th International Conference on Nucleation and Atmospheric Aerosols held in Rolla, Missouri. Supporting Information Available: Additional Guest Editor comments are available as Supporting Information via the Internet at http://pubs.acs.org. Richard H. Heist Robert McGraw Reinhard Strey Guest Editors
